Part of PC-04 — Chemical Thermodynamics

Comparison Note: Reversible vs Irreversible Processes

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FeatureReversible IsothermalIrreversible (Const. PextP_{ext})Free Expansion
Work formulanRTln(V2/V1)-nRT\ln(V_2/V_1)PextΔV-P_{ext}\Delta V00
Heat qqnRTln(V2/V1)nRT\ln(V_2/V_1)PextΔV-P_{ext}\Delta V (for isothermal ideal gas)00
ΔU\Delta U00 (ideal gas, isothermal)00 (ideal gas, isothermal)00 (ideal gas)
ΔSsystem\Delta S_{system}nRln(V2/V1)nR\ln(V_2/V_1)nRln(V2/V1)nR\ln(V_2/V_1)nRln(V2/V1)nR\ln(V_2/V_1)
ΔSuniverse\Delta S_{universe}00>0> 0>0> 0
Work magnitudeMaximumIntermediateZero
RealizabilityTheoretical limitReal processesReal (into vacuum)
Spontaneous?Borderline (reversible)YesYes

Key insight: ΔSsystem\Delta S_{system} is the same for all three (state function), but ΔSuniverse\Delta S_{universe} differentiates reversible from irreversible.

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